Compositions of polycarboxylic acid amides, polyepoxides, and phenolaldehyde condensates



nitc

Sylvan 0. Greenlee, Racine, Wis., assignor to S. (1. Johnson & Son, Inc., Racine, Wis.

No Drawing. Application November 7, 1956 Serial No. 620,814

11 Claims. (Cl. 260-19) This invention relates to new products and compositions resulting from the reaction of mixtures of phenolaldehyde condensates, polyepoxides, and a new class of polycarboxylic acids in regulated proportions to give compositions valuable for use in the manufacture of varnishes, molding compositions, adhesives, molded articles, etc. The invention includes initial reaction mixtures or compositions, as well as intermediate and final reaction products, and methods for their production. More particularly, the polycarboxylic acids are acids derived from bis(hydroxyaryl)substituted acid amides and a monosubstituted aliphatic carboxylic acid.

An object of this invention is the formulation of admixtures of a phenol-aldehyde condensate, a polyepoxide, and a polycarboxylic acid which on further reaction form insoluble, infusible compositions and products.

Another object of the invention is the production of intermediate reaction products of phenol-aldehyde condensates, polyepoxides, and polycarboxylic acids which are capable of further reaction on the application of heat to form insoluble, infusible products.

Another object of this invention is the formulation of phenol-aldehyde, polyepoxide, and polycarboxylic-acid compositions which are hard, extremely tough products possessing good chemical and water resistance.

An additional object of the invention is the production of compositions and intermediate reaction products of phenol-aldehyde condensates, polyepoxides, and polycarboxylic acids which are stable at ordinary temperatures for long periods of time yet may be polymerized to insoluble, infusible products, with or without the use of catalyst, by the application of heat.

Other objects of the invention will appear from the following more detailed description with particular reference to specific illustrative examples.

In the formulation of insoluble, infusible heat conversion products from polyepoxides, one of the problems encountered is that of choosing satisfactory co-reactants in order to obtain the optimum properties in the final composition. An additional problem is encountered in selecting a co-reactant which is miscible and compatible with the polyepoxide in the initial and intermediate stages. Ingredients which have been found to be operable are compositions or compounds containing a reactive hydrogen including certain dicarboxylic acids, amides, and, in some instances, phenol-aldehyde resins.

It has now been observed that the subject polycarboxylic acids are completely miscible with polyepoxides and with phenol-aldehyde condensates. This characteristic, together with other desirable properties, render them an outstanding co-reactantin the formulation of States Patent 2 varnishes, molding compositions, adhesives, molded articles, etc. The polycarboxylic acids used in this invention are fully described in the Greenlee copending application, Serial Number 610,383, filed September 17, 1956, and entitled Polycarboxylic Acid Amides and are the resultant product of a bis(hydroxyaryl)-substituted acid with either an amine or ammonia and the formed amide is then subsequently reacted with a mono-substituted aliphatic organic acid. Because of their configuration, aliphatic-aromatic character, as well as their polyfunctionality, such acids have been found to render particularly valuable polymeric products when co-reacted with epoxides. In addition to acting as a converting agent for the polyepoxides, said acidscontribute to the resinous character of the resultant products and supplement greatly f the hardness, toughness, gloss, and chemical resistance of the co-conversion mixtures with the epoxide. When phenol-aldehyde condensates are used as a third component with the polyepoxides-and polycarboxylic acids, further desirable characteristics are imparted or supplemented The phenol-aldehyde condensates have been found to contribute greatly to the toughness, adhesion, tensile strength, chemical resistance, and rapidity of reaction of these compositions, as well as offering a ready variable in the formulation of specific compositions.

The chemical structure of the subject polycarboxylic acids employed herein may be represented by the reaction products of a monohalo carboxylic acid with an amide of a hydroxyaryl-substitu-ted alkylidene monocarboxylic acid. Such acid amides are obtained by the reaction of ammonia or an ammonia derivative, i.e. an amine with 4,4-bis(4-hydroxyphenyl)pentanoic acid. Polycarboxylic acid amides obtained by reaction saidaryloxy acid with ammonia (I), n-butylamine -(II), and ethylenediamine (III), and their. subsequent reaction'withfmonochloroacetic acid in an alkaline medium are illustrated by the following structural formulas:

4,4-bis(4-hydroxyphenyl)pentanoic acid ammonia p O OH C O OH 4,4-bls (4-hydroxyphenyDpentanolc acid n-butylamine O 0 H2 0 O O H monochloroaoetlc acid CH30-CH2CH2--NHOH2OHZCHQOHQ O CHgC 0 OH II Patented July 7, 1959,

4,4 1; khydioxyphenyhpentauolc acid OCHIOOOH ethylenediamine monochloroaeetic acid CH C 0 OH related compoundsindicates that the carbonyl group of the lt ejto-acid' should be positioned next to a terminal methyl group in order to obtain satisfactory yields. Prior applications, Serial Nos. 464,607 and 489,300, filed October 19 5f1 and February 18, 1955, .respectively, disclos, a number of illustrative compounds suitable for use asjthe Diphenolic Acid and methods of preparing the; 'Ihesematerials, which are referred to' for convenienceby the trademarks of S. vC.'..Tohnson & Son, Incffas Diphenolic Ac id or DPA, consist of the condensation-products of levulinic acid and phenol, substituted phenols, or mixtures thereof. .It is to be understood that the phenolic nuclei'of the Diphenolic Acid may be sublwith any groups which will not interfere with the reactions contemplated herein. For example, the nuclei may be alkylated with alkyl substituents containing from 1-5 carbon atoms as disclosed in Serial No; 489,300 or they maybehalogenated. The Diphenolic Acid derived from substituted phenols, such as the alkylated phenols, aresome timesmore'desirable than the products obtained from unsubstituted phenols'since the alkyl groups provide bette'r organic solvent solubility, flexibility, and water resistance. However, the unsubstituted product is usually' eieanrpu ma Ammonia and a large number of amines are suitable for usein preparing the; amides of the'above-described aryloxy acids, said amides are'subsequently reacted to form the subject polycarboxylic acids. The amines may be aliphatic, aromatic, saturated and unsaturated monoand polyamines. Such amines may be substituted with other functional groups or unsubstituted. It is necessary only that the amine used contain at least one primary or secondary amino group and that the substituted materials. contemplated are those which do not tend to interferewith the reaction of the amino group of the amine'onthe 'carboxyl group of the hydroxyaryl-substituted aliphatic acid.. The aliphatic monoamines andpolyamines may be low molecular weight or high molecular weight compounds. Illustrative monoamines include such materials as the saturated amines: methylaminc, dimethylamine, ethylamine, diethylamine, propylamine, n-prbpylam'ine, di-n-propylamine, butylamine,

o omorrrt knncmomomoal .1 zgxorr qo u fused polynu'clear monoand polyamines.

O CH|C O OH III .amylamine, hexylamine, laurelamine, stearylamine, and

, amine, triethylenetetramine, the polyamines derived from polymerized fatty acids such as dimer acids of linseed fatty acids, soyabean fatty acids, and the polyamines obtained from high molecular weight glycols. Operable aromatic amines include mononuclear, fused and non- I Illustrative compounds are p-phenylen ediamine, aminobenzylphenyleneamin'e, toluene-2,4-diamine, 3,3'-bitolylene, 4,4-diamine, 2,6-diaminopyridine, aniline, naphthylamine, etc. Other operable amines are the resinous amines, such as the monoamine prepared by replacing thecarboxyl group of abietic acid with an amino group. The characteristics of the final reaction product of the amines and the aryloxy carboxylic acids are dependent to a large extent on the selection of the amine to'be used. For example, if a long-chain amine is used, the flexibility is greater than with a short-chain amine or ammonia, whereas the latter imparts increased hardness. For this reason, the final end use of the composition must be considered in selecting the proper amine to be reacted with the bis(hydroxyaryl)substituted alkylidene carboxylic acid. The number of amino groups present should be limited to about 4 since more thanthis number would probably result in highly complex products having limited solvent solubility;

The subject synthetic acidscan be prepared from the Diphenolic Acid amines through reaction with substituted acids which'contain 'up to about 8 carbon atoms. and a single functional group which is capable of reacting .with phenolic hydroxyl groups toform an ether. One'class "of suchcompounds are the irionohalo acids. With this,

group ofthe'monohalo acid'and toforrn an alkali phenoxide with the. phenolic hydroxyl groups of theDiphenolic Acid amide. Under these conditions, the alkali phenoxide will react with the monohalo acidto'form an ether linkage. The reaction may be illustratedby the following formula'r'epre'sen'tingthe reaction of 1 mol of the amide obtained from jthe reaction'of 1 mol of N butylamin'e and 1 mol of 4,4-bis(,4 hydroxyphenyl)pentanoic acid'with 2 mols of monochloroacetic acid through the wellj known; Williamson ethersynthesis.

. OCHsOOsH Although the reactions are usually carried out in an aqueous alkali solution and the resulting polycarboxylic acid precipitated by acidification at the end of the reaction period, some caution must be used in the acidification to avoid breaking the amide. The removal of salt may be carried out by washing with hot water. It may sometimes be desirable to conduct the reaction in the presence of organic solvents or a mixture of an organic solvent and water. Temperatures suitable for the reaction are in the range of 651l0 C.

The substituted acid suitable for use in preparing the instant polycarboxylic acids include aliphatic monohalo acids in which the halogen group is attached to a carbon of the alkyl chain. The alpha-monochloro compounds are usually preferred due to their greater commercial availability and since they readily react in a Williamson ether synthesis with fewer side products being formed. The betaand gamma-halo acids, for example, tend to dehydrohalogenate in the presence of alkali, resulting in lower yields than are obtained from the corresponding alpha-halogen acids. Compounds which are illustrative and particularly advantageous in reactions with the Diphenolic Acid to give the subject polycarboxylic acids are chloroacetic acid and alphachloropropionic acid. Other exemplary acids are 2-chlorocaprylic and S-bromovaleric acids. Epoxy acids such as the glycidic acid, 6,7- epoxy heptanoic acid may also be used but from an industrial standpoint the monohalo acids are preferred. If an epoxy acid is used, the epoxy group will react directly with the hydroxy group without the necessity of forming the alkali phenoxide.

In the preparation of these subject polycarboxylic acid amides it is to be appreciated that there may be some free amine groups in the final composition and also that it may be desirable to etherify only a part of the phenolic hydroxy groups of the parent amide With the substituted monocarboxylic acid, thereby obtaining a composition having free phenolic hydroxyl groups as well as carboxyl groups. Such compounds are also valuable as intermediates in resin manufacture.

A more complete description of the amides suitable for use in preparing the herein described polycarboxylic acids will be found in the Greenlee copending applications, Serial Nos. 507,138, 564,886, and 505,552, filed May 9, 1955, February 13, 1956, and May 2, 1955, respectively. Examples I through VII, inclusive, describe the preparation of a selective group of such amides. The proportions given are expressed as parts by weight unless otherwise indicated. Acid values represent the number of milligrams of KOH required to neutralize a l-gram sample. Amine values represent the number of milligrams of HCl required to neutralize a l-gram sample. The amine and acid values were determined by electrometric titration. Softening points were determined by Durrans Mercury Method (Journal of Oil and Color Chemists Association, 12, 173-175 [1929]).

EXAMPLE I 572 parts DPA were charged to a 1-liter 4-necked fluted flask equipped with thermometer, stirrer, reflux condenser, and dropping funnel. Heat was applied using an electric heating mantle. 70 parts ethylenediamine, as an 86% aqueous solution, was charged to the dropping funnel. When the DPA was melted, a dropwise addition of ethylenediamine was begun with continuous stirring of reactants. Sufiicient heat was maintained to keep the DPA molten. After all the ethylenediamine was added, approximately 30 minutes, a water trap was inserted in the system and the temperature raised to 230 C. Water was being removed during this time. The temperature was held at 230 C. for 5 hours and 40 minutes. The final product had an acid value of 10.7, an amine value of 24.9, and a softening point of 124 C.

6 EXAMPLE n In a 3-necked flask provided with thermometer, mechanical agitator, and reflux condenser attached through a water trap was placed a mixture of 573 parts of 4,4- bis(4-hydroxyphenyl)pentanoic acid and 540 parts of octadecylamine. The reaction mixture was heated for a period of 25 hours at -175 C. with continuous agitation. An additional 37 parts of octadecylamine were added and heating continued at 150-175 C. for a period of 8 hours. The pressure during the last 30 minutes of heating was reduced to 60 mm. The product amounting to 1,087 parts had an acid value of 3.2, an amine value of 1.1 and a softening point of 142 C.

EXAMPLE III In a pressure autoclave provided with a mechanical agitator and a thermometer was placed a mixture of 1145 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid and 585 parts of n-butyl amine. The autoclave was closed and with continuous agitation the mixture heated for 2 hours at -180 C. The reaction mixture was then allowed to cool, and the unreacted butyl amine and Water were removed by distillation, heating the reaction mixture at 173 C. at a reduced pressure of 20 mm. The product, amounting to 1090 parts, had an acid value of 0, an amine value of 1.1, and a softening point of 175 C.

EXAMPLE IV Using the apparatus of Example II, a mixture of 1145 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid and 585 parts of octylamine was heated for a period of 15 hours at 190-210 C. An additional 47 parts of octylamine were added and heating continued for another 12 hours at 190 C. Low molecular weight material was then removed by vacuum distillation at 20 mm. pressure, heating the reaction mixture at 190 C. The product, amounting to 1329 parts, had a softening point of 65 C., an amine value of 2.2, and an acid value of 0.

EXAMPLE V In a 2-liter 3-necked flask equipped with thermometer, stirrer, and reflux condenser was placed 286 parts DPA and 80 parts hexamethylenediamine as a.70% aqueous solution. Upon incorporation of a suitable trap between the condenser and the flask water was distilled from the reaction mixture during a period of 96 minutes. The flask temperature rose to 252 C., 36 parts of water were isolated, and when no more distillate could be obtained, the resultant product, 326 parts of the diamide of 4,4-bis(4-hydroxyphenyl)pentanoic acid and hexamethylenediarnine, was isolated. It had an amine value of 10.5, an acid value of 0, and a softening point of 83 C.

EXAMPLE VI Using the apparatus employed in Example II, a mixture of 573 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid and 205 parts of aniline was heated for 12 hours at 180 C. The temperature was then gradually increased to C. over a 1 hour period. The Water trap was then filled with cyclohexane, and the reaction mixture refluxed for 2 hours at a reaction temperature of 170- 180 C. with the removal of water from the reaction mixture. Final stripping of the reaction mixture was done at a temperature of 180 C. and at a pressure of 60 mm. for 1 hour, resulting in the isolation of 701 parts of the anilide of 4,4-bis(4-hydroxyphenyl)pentanoic acid having a softening point of 107 C., an amine value of 0, and acid value of 7.75.

EXAMPLE VII 5 72 parts DPA were charged to a 1-liter 4-necked fluted flask equipped with thermometer, stirrer, reflux condenser, and dropping funnel. Heat was applied with an electric heating mantle. 146 parts triethylenetetramine were charged to the dropping funnel. When the DPA was melted, dropwise addition of ethylenediamine was begun with continuous stirring. Suflicient heat was maintained to keep the DPA molten. After all the triethylenetet'ramine had been added, approximately 1 hour, a water trap was inserted in the system and the temperature raised to 230 C. Water was being removed during this time. The temperature was held at 230 C. for 6 hours. The final reaction product had an acid value of 0, an amine value of 84.9, and a softening point of 116 C.

Examples VIII through XIV illustrate the preparation of polycarboxylic acids by the reaction of Diphenolic Acid amides with halo aliphatic organic acids. The quantities of materials given are parts by weight unless otherwise indicated. V

EXAMPLE VIII In a flask equipped with a mechanical stirrer, a reflux condenser and a thermometer was placed 149 parts of the Diphenolic Acid amide of Example I and 40 parts of sodium hydroxide dissolved in 200 parts of water. With continuous agitation at a temperature of 82-85 C., 94.5

parts of monochloroacetic aciddissolved in 40 parts of sodium hydroxide and 200 parts of water were added slowly. The preparation of the solution of chloroacetic acid in 40 parts of sodium hydroxide and 200 parts of water was made at C. to avoid hydrolysis before being used in the reaction. With continuous agitation the reaction mixture was held at 82-85" C. for 2 hours and 20 minutes. The reaction mixture was neutralized to a pH of 4.2 with concentrated HCl and held at this pH with continuous agitation for a period of 1 hour. After removing the mother liquor, the resulting product was washed 3 times with hot water and the last traces of water removed by heating to 130 C. The product had an acid value of 175 and a softening point of 92 C.

EXAMPLE IX By the same procedure as that used in Example VIII, 134 parts of the Diphenolic Acid amide of Example II, 60 parts of sodium hydroxide in 100 parts of water, and 300 parts of dioxane were treated with 142 parts of monochloroacetic acid dissolved in 60 parts of sodium hydroxide and 200 parts of water. The product had an acid value of 144.

EXAMPLE X As in Example VIII, treatment of 85 parts of the Diphenolic Acid amide of Example III dissolved in 21 parts of sodium hydroxide and 150 parts of water with 48 parts of monochloroacetic acid dissolved in 20 of sodium hydroxide and 150 parts of water gave a product having an acid value of 170.

8 EXAMPLE XI As in Example VIII, treatment of 99 parts of the Diphenolic Acid amide of Example IV dissolved in 61 parts of 'sodiumhydroxide and 175 parts of water with 141 parts of monochloroacetic acid dissolved in 61 parts of sodium hydroxide and 200 parts of water gave a product having an acid value of 160.

EXAMPLE )GI As in Example VIII, treatment of 163 parts of the Diphenolic Acid amide of Example V dissolved in 51 parts of sodium hydroxide and 150 parts of water with 118 parts of monochloroacetic acid dissolved in 51 parts of sodium hydroxide and 200 parts of water gave a product having an acid value of 210.

EXAMPLE XIII As in Example VHI, treatment of 126 parts of the Diphenolic Acid amide of Example VI dissolved in 41 parts of sodium hydroxide and 150 parts of water with 94.5 parts of monochloroaceticacid dissolved in 41 parts of sodium hydroxide and 200 parts of water gave a product having an acid value of 158.

EXAMPLE XIV Treatment as in Example VIII of 170.5 parts of the Diphenolic Acid amide of Example VII dissolved in 61 parts of sodium hydroxide and 150 parts of water with 142 parts of monochloroacetic acid dissolved in 61 parts of sodium hydroxide and 200 parts of water gave a product having an acid value of 215.

Illustrative of the epoxide compositions which may be employed in this invention are the complex epoxide resins which are polyether derivatives of polyhydric phenols with such polyfunctional coupling agents as polyhalohydrins, polyepoxides, or epihalohydrins. These compositions may be described as polymeric polyhydric alcohols having alternating aliphatic chains and nuclei connected to each other by ether linkages containing terminal epoxide groups and free from functional groups other than epoxide and hydroxyl groups. It should be understood that significant amounts of the monomeric reaction products are often present. This would be illustrated by Ia to IIIa below where n equals zero. Preparation of these epoxide materials as well as illustrative examples are described in US. Patents 2,456,408, 2,503,726, 2,615,007, 2,615,008, 2,688,805, 2,668,807, and 2,698,315. Wellknown commercial examples of these resins are the Epon resins marketed by the Shell Chemical Corporation. Illustrative of the preparation of these epoxide resins are the following reactions wherein the difunctional coupling agent is used in varying molar excessive amounts:

Polyhydric phenol and an eplhalohydrin bis(hydroxyphenyl)isopropylldene excess epichlorohydrin Polyhydrlc phenol and a polyepoxlde bis(hydroxyphenyl)lsopropylldene excess butylene dioxide 0 HkHCHOHCH O lkah I CH,OHCH O oCHgOHOHCH1-0 OCH OHCH;

Cg CH1 n C CH3 Ia aqueous alkali l l OCHQCHOHGHOHCHQO OCH CHOHOHCH; 2 E O /O\ C CH; CH; CH;

v i I M f" v aqueous Polyhydric phenol and a polyhalohydrln bis (hydroxyphenyl)isopropylldene excess alpha-glycerol dlchlorohydrin kg;

0 0 at F l 0 H; HCH O OCH GHOHOH 00H, HCH,

0 CH 'n C CH, IIIa As used in the above formulas, n indicates the degree of polymerization said polymerization being dependent on the molar ratio of reactants. As can be seen from these formulas, the complex epoxide resins used in this invention contain terminal epoxide groups and alcoholic hydroxyl groups attached to the aliphatic portions of the resin, the latter being formed by the splitting of epoxide groups in the reaction of the same with phenolic hydroxyl groups. Ultimately, the reaction with the phenolic hydroxyl groups of the polyhydric phenols is generally accomplished by means of epoxide groups formed from halohydrins by the loss of.hydrogen and halogen as shown by the following equation: x

Other epoxide compositions which may be used include the polyepoxide polyesters which may be. prepared by esterifying tetrahydrophthalic anhydride with a glycol and epoxidizing the product of the esterification reaction.

In the preparation ofthe polyesters, tetrahydrophthalic acid may also be used as well as the simple esters of tetrahydrophthalic acid such as dimethyl and diethyl esters. There is a tendency with tertiary glycols for dehydration to occur under the conditions'used for esterification so that the primary and secondary glycols are the most satisfactory in the polyester formation. Glycols which may be used in the preparation of this polyester composition comprise, in general, those glycols having 2 hydroxyl groups attached to separatecarbon atoms and free from functional groups which would interfere with the esterification or epoxidation reactions. These glycols include such tglycols as ethylene glycol, diethylene glycol, triethylene glycol, tetramethylene glycol, propylene glycol, polyethylene glycol, neopentyl glycol, and hexamethylene glycol. Polyepoxide polyesters may be prepared from these polyesters by epoxidizing the unsaturated portions of the tetrahydrophthalic acid residues in the polyester composition. By properly proportioning reactants in the polyester formation and regulating the epoxidation reaction, polyepoxides having up to 12 or more epoxide groups per molecule may be readily prepared. These polyepoxide polyester compositions as well as their preparation are more fully described in a copending application having Serial No.

53,323, filed April 22, 1955.

Polyepoxide compositions useful in this invention also include the epoxidized unsaturated natural oil acid esters, including the unsaturated vegetable, animal, and fish oil acid esters made by reacting these materials with various oxidizing agents. These unsaturated oil acid esters are long chain aliphatic acid esters containing from about 15 to 22 carbon atoms. These acids may be esterified by simple monohydric alcohols such as methyl, ethyl, or decyl alcohol, by polyhydric alcohols such as glycerol, pentaerythritol, polyallyl alcohol, or resinous polyhydric alcohols. Also suitable are the mixed esters of polycarboxylic acids and long chain unsaturated natural oil acids with polyhydric alcohols, such as glycerol and pentaerythritol.

These epoxidized oil acid esters may contain more than 1 up to 20 epoxide groups per molecule. The method of epoxidizing these unsaturated oil acid esters consists .of treating them .with variousoxidib ing agents, such as the organic peroxides and the peroxy acids, or with one of the various forms of hydrogen peroxide. A typical procedure practiced in the art consists of using hydrogen peroxide in the presence of an organic acid, such as acetic acid and a catalytic material, such as sulfuric acid. More recently epoxidation methods have consisted of replacing the mineral acid catalyst 1 with a sulfonated cation exchange material, such as the sulfonated copolymer of styrene divinylbenzene.

The epoxide compositions which'may be used in preparing the compositions of this invention also include aliphatic polyepoxides which may be illustrated by the products obtained by polymerizing allyl glycidyl ether.

polyhydric alcohol with an epihalohydrin in the presence of a suitable catalyst and in turn dehydrohalogenating the product to produce the epoxide composition. The production of these epoxides may be illustrated by the reaction of glycerol with epichlorohydrin in the presence of boron trifluoride followed by dehydrohalogenation with sodium aluminate as follows:

J J(\ BF:

HOE +3 HgCHCHgCl HQOH O CHgOCHgCHOHCHaCl CHQOCHQCHCHQ O NaAlOg CHOCHZCHOHCHQC). HOCH; HCH;

0 g\ CHgOCHaOHOHCHrCl CHgOQHg HCH,

It is to be understood that such reactions do not 'give pure compounds, and that the halohydrins formed and be characterized by the presence of hydroxyl groups and halogens. Dehydrohalogenation 'aifects only those hydroxyl groups and halogens which are attached to adjacent carbon atoms. Some halogens may not be removed in this step in the event that the proximate carbinol group has been destroyed by reaction with an epoxide group. Thesehalogens are relatively unreactive,

and are not to be consideredas functional groups in the conversion of the reaction mixtures of this invention.

The preparation of a large number of these mixed polyepoxides is described in the Zech patents, U. S. 2,538,072, 2,581,464, and 2,712,000; Still other polyepoxides which have been found to be valuable are such epoxide corn positions as diepoxy butane, diglycid ether, and epoxidized polybutadiene.

Immediately following will be 'a. description or illus tration of preparations of polyepoxides' which be used in examples of compositions of this invention.

The complex resinouspolyepoxid e's .used in the exam-:

In addiples and illustrative of the commercially prepared products of this type are-the Epon-resins marketed-by Shell- Chemical Corporation. The following table gives the properties of some Epon resins which are prepared by the condensation in the. presence of alkali of bis(4-hydroxphenyl)isopropylidene witha molar excess of epi-z chlorohydrin in varying amounts.

1 Based on 40% nonvolatile in butyl carbitol at C.

Examples'XV through XVII describe the preparation of typical polyepoxide polyesters.

EXAMPLE XV Preparation of polyester from tetrahydrophlhalic anhydride and ethylene glycol In a 3-necked flask provided with a thermometer,-

mechanical agitator, -=and a reflux condenser attachedthrough a water trap was placed a mixture of 3 mols of tetrahydrophthalic anhydride and Zmols of'n-butanol.

Aftermelting the tetrahydrophthalic anhydride-in the presence of the .butanol, 2 mols of ethylene glycol were added- The reaction mixture was gradually heated with agitation-to 225 C. atwhich'point a s-uflicient amount of -xylenewas added to give refluxing at esterificationtemperature. The reaction mixture'was then heated with continuous agitation at 225235 C.- until an acid value of 4.2 was obtained. This product gave an iodine value of 128.-

Epoxidation of the polyester resin- In a 3-necked flask provided with a thermometer, a

mechanical agitator, and a reflux condenser. was placed 107 parts of the dehydrated acid form of a cation exchange resin (Dowex 5 0-X8, 5 0-100 mesh, Dow Chemical Company, a sulfonated styrene-divinylbenzene copolymer containing about 8% divinylbenzene, the percent divinylbenzene serving to control the amount of crosslinkage;= 1 The Dowex resins are discussedin publications entitled Ion Exchange Resins No. l and Ion Exchange Resins No. 2, copyright 1954 by Dow Chemical-Company, the publications having form number Sp32-254 and Sp31-354, respectively) and parts glacial .acetic acid... The mixture of cationexchange resin .and acetic acid was allowed to stand YuntiLthe resin had-completely taken upthe acid. To this mixture was.

added-ZOOparts of the polyester resin dissolved in an.

equal weight of xylene. To the continuously agitated ree action mixturewasxadded dropwise over a period of 45.2 minutes .to 1 hour, .75. parts of. 50% hydrogen peroxide;

The reaction temperature was. heldat C} requiring the. application of some external heat... (In:some:prepa rations involvingother polyester resins, 'suflicient exo-x.

thermicheat is produced during the addition of hydrogen peroxidei'so'that no external heat is required, or. even some external cooling may-be required.) Thereaction was .continued at 60 C. until a milliliter sample :of'then.

reactionmixture analyzed less than 1 milliliter of 0.1 N

sodium thio'sulfate in 'an iodometric determination of. hy-

drogemperoxide. The product was then filtered, finally non-volatile. of this solution amounting .to 400 parts-was 50. The resulting 400 parts of solution were thoroughly mixed. with parts of the:.dehydrated basictform *of ammonium type Dowex 1 is a styrene-divinylbenzene wpolymer illustrated by: thcifotmulaRRgNtOHrzwherc R represents the styrene-divinylbenzene matrix and R is a methyLigroup, manufactured by the Dow Chemical Company). The resulting mixture was then filtered followed by pressing as much of the solution as possible from theanionexchange resin cake. This product had an. acid value of 4.5 and an epoxide equivalent of 288 based on a nonvolatile resin content of 42.0%. The epoxide values as discussed herein were determined by refluxing for 30 minutes a Z-gram sample with 50 milliliters of pyridine hydrochloride in excess pyridine. (The pyridine hydrochloride solution was prepared by adding 20 milliliters of concentrated HCl to a liter of pyridine.) After. cooling to room temperature, the sampleis then EXAMPLE XVI EXAMPLE XVII The process of Example XV was followed to'obtain a polyestermesin from 1.1 mols.of tetrahydrophthalic anhydride,..-1 mol-of l,4-butanediol and 0.2 mol of n-butanol; Theproduct hadanacid value of. 8.6. This polyester resin was. epoxidizedin'thesame manner to give an epoxide equivalent-weigltof292' and an acid value 0f"5.2 on the nonvolatilecontent. The nonvolatile conr tent of this resin solution was 41.9%.

Examples-.XVIII describe the preparation of epoxidized vegetable oil acid esters.-

EXAMPLE XVIII Epoxidizedsoyabetmoil acidmodified alkyd resin (1. PREPARATION OF ALKYD RESIN To a kettle provided with a condenser was added 290 parts of white, refinedsoyabean oil. While bubbling a continuous stream of nitrogen through this oil the temperature was raised, to 250? C.,' at which temperature 0.23 part oflithange was added and the temperature held at 250C. for 5 minutes. While holding the temperature above 218 C., 68- par-ts of technical pentaerythritol were added,. 'after which the temperature was raised to 238C. andhelduntila mixture of 1 part of the product and 2 /2 parts of methyl, alcohol showed. no insolubility (about 15 minutes). At this point 136 parts of phthalic anhydride were added and the temperature gradually raised to 250- C. and heldat this temperature for 30 minutes. At thispoint the condenser 'was removed from the kettle and the pressure reduced somewhat by attaching to a water aspirator evacuating system.- With continuous agitationthe mixture was held at 250 C. until the acid value, had reached 10.5. resin was thinned with xylene to-48% nonvolatile content having a viscosity of .H (Gardner bubble viscosimeter).

b. EPOXIDATION OF A SOYABEAN OIL ACID MODI- FIED ALKYD RESIN I In a 3-necke'd flask provided witha thermometer, a mechanical agitator and a reflux condenser was placed 70 parts of dehydrated acid form of a cation exchange resin (Dowex 50-X-8) and 15 parts glacial acetic acid. The mixture of cation-exchangeresin and acetic acid was allowed-tostanduntilthe resin had completely taken up the acid. To this rnixture was added 315 parts of the alkyd-resin solutiondescribed-in the' above paragraph and parts of xylene.-; -:.To"'thecontinuouslyagitated reac- :tion mixture was added dropwise 38 parts of 50% hydroback-titrated with'standard alcoholic sodium hydroxide. 15-

At this point the gen peroxide. The reaction temperature was held at 60 C. until a milliliter sample of the reaction mixture analyzed less than one milliliter of 0.1 N sodium thiosulfate in an iodometric determination of hydrogen peroxide. The product was then filtered, finally pressing the cation exchange resin filter cake. The epoxide equivalent on the nonvolatile content was 475.

In order to remove the free acidity from the epoxidized product, 400 parts of the solution were thoroughly mixed with 110 parts of the dehydrated basic form of Dowex 1 (an amine type anion exchange resin). The resulting mixture was then filtered, followed by pressing as much of the solution as possible from the anion exchange resin cake.

EXAMPLE XIX Epoxidized soyabean oil EXAMPLE XX In a reaction vessel provided with a mechanical stirrer and external cooling means was placed 276 parts of glycerol and 828 parts of epichlorohydrin. To this reaction mixture was added 1 part of 45% boron trifluoride ether solution diluted with 9 parts of ether. The reaction mixture was agitated continuously. The temperature rose to 50 C. over a period of 1 hour and 45 minutes at which time external cooling with ice water was applied. Thetemperature was held between 50 and 75 C. for 1 hour and 20 minutes. To 370 parts of thisproduct in a reaction vessel provided with a mechanical agitator and a reflux condenser was added 900 parts of dioxane and 300 parts of powdered sodium aluminate. With continuous agitation this reaction mixture was gradually heated to- 92" C. over a period of 1 hour and 50 minutes, and. held at this temperature for 8 hours and 50 minutes. After cooling to room temperature, the inorganic material was removed by filtration. The dioxane and low boiling products were removed by heating the filtrate to 205 C. at.20 mm. pressure to give a pale yellow product. The epoxide equivalent of this product was determined by treating a l-gram sample with an excess of pyridine containing pyridine hydrochloride (made by adding 20 cc. of concentrated hydrochloric acid per liter of pyridine) at the boiling point for 20 minutes and back-titrating the excess pyridine hydrochloride with 0.1 N sodium hydroxide using phenolphthalein as'indicator and considering one HCl as equivalent to one epoxide group. The epoxide equivalent on this product was found to be 152.

EXAMPLE XXI 'In a 3-necked flask provided with a thermometer, a mechanical agitator, a reflux condenser and a dropping funnel was placed 402 parts of allyl glycidyl ether. With continuous agitation the temperature was raised to 160 C. at which time one part of a solution of methyl ethyl ketone peroxide dissolved in diethyl phthalate to a 60% content was added. The temperature was held at 160-165" C. for a period of 8 hours, adding one part of the methyl ethyl ketone peroxide solution every 5 minutes during this 8-hour period. After the reaction mixture had stood overnight, the volatile ingredients were removed by vacuum distillation. The distillation was started at 19 mm. pressure and a pot temperature of 26 C. and volatile material finally removed at a pressure of 3 mm. and a pot temperature of 50 C. The residual product had a molecular weight of 418, and equivalent weight to epoxide content of 198, the yield amounting to 250 parts.

The phenol-aldehyde condensates used in making the compositions herein described are those formed by the reaction of phenols and aldehydes, which contain reactive phenolic hydroxyl groups. Phenol and formaldehyde react to form a variety of reaction products, depending upon the proportions and conditions of reaction. These include products such as phenol alcohols having both phenolic and alcoholic hydroxyl groups and products of the diphenolmethane type containing phenolic hydroxyl groups only. The condensation of phenol and formaldehyde can be carried out with the use of acid or alkaline condensing agents and in some cases by first combining the aldehyde with an alkali such as ammonia to form hexamethylenetetramine and reacting the latter with the phenol. The phenol-aldehyde resins at an initial or intermediate stage of reaction are intended to be included in the term phenol-aldehyde condensates as used herein.

In general, the phenol-aldehyde condensates should not have their condensation carried so far as to become insoluble and nonreactive. It is preferred in the preparation of the instant compositions that they be used at an intermediate stage or at a stage of reaction such that they contain reactive phenolic hydroxyl groups or both phenolic and alcoholic hydroxyl groups. This is desirable in order to permit a proper blending of the phenolaldehyde condensate with the polyepoxides and monohydric alcohol esters of aryloxy-substituted acids for subsequent reaction therewith.

The phenol-aldehyde condensates may be derived from mononuclear phenols, polynuclear phenols, monohydric phenols, or polyhydric phenols. The critical requirement for the condensate is that it be compatible with the polyepoxides and polycarboxylic acid amides or with the two reactants in a solvent used as a reaction medium. The phenol-aldehyde condensate which is essentially a poly methylol phenol rather than a polymer may be used in the preparation of the new phenol-aldehyde, polyepoxide, polycarboxylic acid amide condensation products or it may be used after further condensation, in which case some of the methylol groups are usually considered to have disappeared in the process of condensation. Various so-called phenolic resins which result from the reaction of phenols and aldehydes, and particularly from common phenols or cresols and formaldehyde, are available as commercial products both of an initial and intermediate character. Such products include resins which are readily soluble in common solvents or readily fusible so that they can be admixed with the epoxides and monohydric alcohol esters of aryloxy-substituted acids and reacted therewith to form the products of this invention.

In selecting a phenol-aldehyde condensate one may choose either the heat-converting or the permanently fusible type. For example, the formaldehyde reaction products of such phenols as carbolic acid, resorcinol, and

bis(4-hydroxyphenyl) isopropylidene readily convert to infusible, insoluble compositions on the application of heat. On the other hand, some of the para alkylated phenols, as illustrated by p-tert-butylphenol, produce permanently fusible resins on reaction with formaldehyde. Even though fusible condensates are employed, however, insoluble, infusible products result when they are heated in combination with the epoxides and the monohydric alcohol esters of arylox-y-substituted acids described.

Examples XXII through XXIV describe the preparation of a selective group of phenol-aldehyde condensates which are used in combination with the polyepoxides and polycarboxylic acid amides.

EXAMPLE XXII Condensation of bisphenol [bis(para-hydr0xyphenyl) isopropylz'dene] with formaldehyde In a 3-liter 3-necked flask provided with a mechanical agitator, a thermometer, and a reflux condenser was placed 912 parts of Bisphenol A, 960 parts of 37% aqueous formaldehyde, and 2.3 parts of oxalic acid. With continuous agitation, the reaction mixture was heated to the refiux temperature and refiuxingcontinuedfor a period of 1 hour.. After permitting the reaction mixture to coolv to around 50 C. the water layer was removed by decantation. The phenol-formaldehyde layerwas then washed three times with water which in each case was removed by decantation. The last portion of water .was removed by distillation at reduced pressure using a water aspirator system which gave pressure around 30-40 mm. The temperature during the removal of this last portion of water ranged from 70-90 C. The product, amounting to 1065 parts, was. a clear, heavy, syrupy material.

EXAMPLE XXIII Reaction of p-tertiary butylphenol with formaldehyde The procedure of preparation, including the dehydration step, was the same as that used in Example XXII. A mixture of 1000 parts of p-tert-butylphenol,,1067 parts of 37% aqueous formaldehyde, and ;parts of sodium hydroxide was used to give a final yield of 1470 parts of a clear, almost colorless syrupy product.

EXAMPLE XXIV Reaction of phenol with formaldehyde Again a reaction procedure including the dehydration step was the same as that used in Example XXII. A mixture of 658 parts of phenol, 1400 parts of 37% aqueous formaldehyde, and 6.6 parts of sodium hydroxide was used to give a final yield of 1168 parts of a clear, syrupy product.

The reaction between the epoxides, the phenol-aldehyde condensates, and the polycarboxylic acid amide described is efiected by heating a mixture of the same at elevated temperatures, usually in the range of 100200 C. Usually the addition of a catalyst is unnecessary; however, in certain cases it may be desirable to use small amounts of catalyst, such as the boron trifluorride adducts, sodium phenoxides, sodium alcoholatc, or sodium salts ofthe phenol-aldehyde condensates.

The mixture of epoxides, phenol-aldehyde condensates,

and polycarboxylic acid amides is of utility at initial 'or I varying intermediate stages of the reaction. Thus initial or intermediate reaction products which are soluble in common solvents may be-blended-in solution in proper concentration and the solutions then used-as a coating or impregnant for fabrics or paper or for the formation of protective coating film's. Heat may be then applied to remove the solvent and'bring about polymerization to the insoluble, infusible state. In certain other instances, as for molding compositions, the initial mixture or intermediate reaction product of the three reactants described may be used without a solvent, giving directly a composite which on the application of heat converts to a final infusible product.

For the preparation of a composition such as a semiliquid adhesive, it is advantageous to usesyrupy phenolaldehyde condensates which are essentially uncondensed methylol phenols, a relatively low melting polyepoxide and a polycarboxylic acid amide having a softening point (Durrans Mercury Method) below about 100 C. For various other applications solid or very viscous compositions are desirable, in which case partially polymerized mixtures would be advantageously used.

In making the new compositions and products herein described, the epoxides, the phenol-aldehyde condensates, and the polycarboxylic acid amides may be used with each other in regulated proportions without the addition of other materials. However, for certain end uses, additional ingredients are often advantageously employed including filling and compound materials, pigments, etc. For the compositions which tendto give somewhat brittlev products on heat conversion to the insoluble, infusible state, plasticizers maybe added. However, in most instances, it is possible to regulate the proportions ofthe threereacting ingredients so as. to obtain products of suitable flexibility, obviating the necessity for plasticizers.

The polymerization of. mixtures. of epoxide, phenolaldehyde condensateand polycarboxylic acid amides may involve several chemical reactions. It will be appreciated that the". reactions involved are very complex and the.

extent to which each takes place will. vary with the temperature and time of heat treatment andwith thenature of the three reactants employed; While it is not intended tobelimited by any theoretical explanation of the exact nature of these reactions, it seems probable that conversion to the final polymeric products by reaction between the three reactants described involves direct polymeriza- :properties, such as high resistance to oxidation, water,

alkali, acids, and organic solvents. It has also been observed that the final conversion products possess unusually good adhesion to most surfaces including metal, glass, wood, and plastics. outstanding adhesion to a wide variety of surfaces which gives the subject products high potential value for use in formulating adhesives. Its superior adhesion to surfaces is also of extreme value informulating protective coating films for use on many types of surfaces. The adhesion characteristics are probably due to the fact that even in the converted, infusible state the compositions contain a high percentage of highly polar groups, such asalcoholic hydroxyl groups, ether groups, and phenolic Despite the high percentage of polar hydroxyl groups. groups in-the insoluble, infusible products of this inven-' tion, tolerance for water'is unusually low, apparently due tothe-high molecular weight and the rigidcrosslinked" structure of the final composition.

The present invention provides. a wide range of reaction compositions and products, including initial mixtures of the aforesaid epoxides, phenol-aldehyde condensates, and

polycarboxylic acid amides, their partial or intermediate reaction products, and compositions containing such intermediate reaction products as well as final reaction products. In general, the initial mixtures, as Well as the intermediate reaction products, unless too highly polymerized, are soluble in organic solvents used in lacquers, such as ketone andester solvents.

The reaction mixtures andfinal reaction-products of this inventionmay be prepared by using varying propontions of polyepoxide, phenol-aldehyde condensate, or

polycarboxylic acid amides. The quantity of reactants employed in a given instance will depend upon the characteristics desired in the final product. For example, if an alkali-sensitive coating is desired, an excess of polycarboxylic acid could be used, or for certain other appli cations, it may be desirable to use a large amount of phenol-aldehyde condensate to increase the'chemical re-- sistance. In still other instances, flexibility may be increased in a given composition by employing a hard polycarboxylic acid and a relatively large amount of linear long-chain'polyepoxides. Alternatively, flexibilitymay be imparted-bylarge-amounts of a soft polyepoxide in combination with a hard polycarboxylic acid amideand a phenol-aldehyde condensate.- In general, while a large excess of polyepoxide or polycarboxylic acid may beapplicable for specific applications, most often equivalent or near equivalent ratios of polyepoxide or polycarboxylic acid areernployed. It has been found, therefore, thatthe 1:2 to 2:1'1'ati0s' give the best over-all- It is this physical property of characteristics, although ratios as high as 1:10 and 10:1 may be used. Equivalents as herein expressed refer to weight of polyepoxide per epoxide group, in the instance of the polyepoxides, and the weight of the acid per car- 18 (1) an amide of 4,4-bis(4-hydroxyphenyl) -pentanoic acid containing not more than about 4 NH groups and (2) an alpha-monohalo, monocarboxylic saturated aliphatic acid containing up to about eight carbon atoms; (B) a boxyl group, in the instance of the polycarboxylic acid. 5 a fusible phenol-aldehyde condensate; and (C) an organic The phenol-aldehyde condensates are employed to makepolyepoxide containing an average of more than one up from 5-85% 'of the composition by weight, but it is oxirane group and being free of groups reactive with usually sufficient to use about of the aldehyde consaid amide and said condensate other than densate on a weight basis. The phenol-aldehyde cony r xyl, r yl and o anedensates impart in most instances increased hardness, 10 Th position of cla ml wherein Said acid (2) increased water and alkali resistance, acceleration of the is OhlOraCfitiC acid conversion, and, in many instances, increased flexibility. Th comp i n of claim 1 wherein said acid (2) Examples XXV through LI, inclusive, illustrate the con- 18 alpha'chloropmplohic aclth version of compounds of polyepoxides, phenol-aldehyde T C P H f Cla m 1 wh rein (C) is a 00mcondensates, and polycarboxylic acid amides to insoluble, ple x resinous polyepoxide which is a polymeric polyhyinfusible protective coating films. For these preparations, dllc alcohol having alternating aliphatic chains and the polyepoxides, phenol-aldehyde condensates, and polyar0h1ati nuclei United through ether Oxygen and tamicarboxylic acid amides were dissolved in a suitable solvent Dating n OXiYaHC S1lhSt1tIlted Chains. to a nonvolatile content of 40-60%. The polycarboxylic 5. 'I:he composition of claim 1 wherein (C) is an acid amides and polyepoxides were dissolved in methyl 20 epoxldllfid P01343946r 0t tetrahydl'ophthalic acid and a ethyl ketone, or dimethyl formamide. The phenol-aldeg y wherein the P Y Oxygen atoms are each limited hyde condensates were dissolved in a mixture of butanol to adjacent Carbon atoms in the nucleus of Said acidand methyl ethyl ketone. Solutions of polyepoxides, composition of claim 1 wherein is P yphenol-aldehyde condensates and polycarboxylic acid functional epoXldiZed ester of all ethylellicauy uIlsa-tuamides were admixed and spread on glass panels in thin rated natural fatty Oil acid containing about 15-22 films of .00 wet thickness for h at tr atm t, Th carbon atoms, and being free of groups reactive with said compositions prepared in this manner are tabulated acid amlde and Said Condensate other than below. Proportions as expressed in the tables refer to Xirane. parts by weight based on a nonvolatile content. 7. A composition of matter obtained by heating a Films Resistance Parts of Polye- Parts of Polyear- Parts of Aldehyde Baking Example No. poxide boxylic Acid Condensate Schedule,

Min./ 0. Boiling Water 5% Aqueous N aOH at 25 0.

7.6, Epon 1001..- 5. 1.3, Ex. /175 3 hrs., 30 min 72 hrs. 11.5, Epon 1004.--- 5. 1.7, Ex. 30/175 3 hrs., 30 min 168 hrs. 17.0, Epon 1007 2. 2.0, Ex. 30/175 15 min 168 hrs. 4.8, Epon 864 5. 1.0, Ex. 10 hrs. 6.3, Epon 854 5. 1.1, Ex. 0/ 72 hrs. 2.5, Epon 1001. 2. 5.0, Ex. 2 hrs., 30 mm 5.5, Ex. V 5. 1.1, Ex. hr. 4.3, Ex. 5. E 0.9, Ex. 10 min. 4.5, Ex. 5. 1.0, Ex. 2 hrs., 30 min. 4.7, Ex. 5. 1.0, Ex. min. 4.2, Ex. 5. 0.9, Ex. 1 hr., 30 min. 0.2, Ex. 5. 1.1, Ex. min. 8.0, Ex. 1. 0.5, Ex. min. 1.0, Ex. 1. 8.0, Ex. 45 min 4.1, Ex. 5. 0.9, Ex. 30 min. 6.9, Ex. 5. 1.2, Ex. 4 hrs, 30 min. 5.1, Ex. 5. 1.0, Ex. 10 min. 3.4 Ex. 5. 0.8, Ex. 2 hrs., 30 min. 6.9, E 5. 1.2, Ex. 2 hrs., 30 min. 8.0, E 1. 0.5, Ex. 2 hrs, 30 min. 2.4, E'. 5. 0.7, Ex. 30 min. 2.9, Ex. XXI 5.0, Ex. XIII- 0.8,Ex. 168hrs. 2.3, Ex. XX 5 E .X 0.7, Ex. 15 min. 2.0, Ex. XXI 50, Ex. IX 0.8, Ex. 45 min. 2.9, Ex. XX 5.0, Ex. XII 0.8, Ex. 10 min. 1.0, Ex. XX 8.0, Ex. IX 1.0, Ex. 45min. 1.0, Ex. XX 1.0,Ex.XII 8.0, Ex. 45min.

EXAMPLE LII mixture consisting essentially of (A) a polycarboxylic 5 parts Epon 864, 10 parts Example X, and 85 parts Example XXIII were charged to a reaction vessel and heat converted 30 minutes at 175 C. to give a hard, tough, infusible, and insoluble product.

EXAMPLE LIII 25 parts of Example XVIII, 25 parts of Example XII, and parts of Example XXIII were changed to a reaction vessel and heat converted 30 minutes at 175 C. to give a hard, tough, infusible, and insoluble porduct.

It should be appreciated that while there are above disclosed but a limited number of embodiments of this invention, it is possible to produce still other embodiments without departing from the inventive concept herein disclosed.

It is claimed and desired to secure by Letters Patent:

1. A composition of matter obtained by heating a mixture consisting essentially of (A) a polycarboxylic acid amide obtained by heating in the presence of alkali acid amide obtained by reacting in the presence of alkali 1) an amide of 4,4-bis(4-hydroxyphenyl)-pentanoic acid and an organic amine containing not more than about four amino groups and (2) an alpha-monohalo, monocarboxylic saturated aliphatic acid containing up to about eight carbon atoms; (B) a fusible phenol-aldehyde condensate; and (C) an organic polyepoxide containing an average of more than one oxirane group and being free of groups reactive with said amide (A) and said condensate (B) other than hydroxyl, carboxyl and oxirane.

8. The composition of claim 7 wherein said organic amine is an aliphatic mono-amine.

9. The composition of claim 7 wherein said organic amine is an aliphatic polyamine.

10. The composition of claim 7 wherein said organic amine is an aromatic amine.

11. A composition of matter obtained by heating a mixture consisting essentially of (A) a polycarboxylic acid amide obtained by reacting in the presence of alkali 2,893,965 19 2O (1) an amide of a pentanoic acid consisting essentially and being free of groups reactive with saidamide (A) of 4,4-bis(4-hydroxyaryl)pentanoic acid wherein the hyand said condensate (B) other than hydroxyl, carboxyl drox'yaryl'r-a'dical-is a hydroxyphenyl radical and is free and oxirane. from substituents other than alkyl groups of from 1'5 carbon atoms and an organic amine containing not more 6 fe'l'ems C te in thefile of'this patent than about four amino groups and (2) an alpha-monow halo, monocarboxylic saturated aliphatic acid contain- UNITED STATES PATENTS ing up to about eight carbon atoms; '(B) a fusible phenol- 7 2,521,911 Greenlee Sept. 12, 1950 aldehyde condensate; and (C) an Organic polyepoxide 2,712,535 Fisch July 5, 1955 containing an average of more than one oxirane group 10 'UNTTED STATES PATENT OFFICE fiertificate of Sorrection Patent No. 2,893,965 July, 7, 1959 Sylvan O. Greenlee It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 33, for reaction reed -reaeting; column 4, right-hand portion of Formula III, for

OCHsCOOH O CH2COOH Ha read -43 CH3 OHBCOOE (SOHzOOOH column 4, line 46, for amines read amides-; column 7, line 49, after the numeral 20 insert -parts column 9, line 57, for the Serial No. 53,323 read -503,323; column 11, line 13, 1n the table, second column thereof, second item, for 64.76 read -6476.

Signed and sealed this 7th day of June 1960.

Attest:

KARL H. AXLINE, Attestz'ng Oflicer.

ROBERT C. WATSON, Gammz'ssz'oner of Patents. 

1. A COMPOSITION OF MATTER OBTAINED BY HEATING A MIXTURE CONSISTING ESSENTIALLY OF (A) A POLYCARBOXYLIC ACID AMIDE OBTAINED BY HEATING IN THE PRESENCE OF ALKALI (1) AN AMIDE OF 4,4-BIS(4-HYDROXYPHENYL)-PENTANOIC ACID CONTAINING NOT MORE THAN ABOUT 4>NH GROUPS AND (2) AN ALPHA-MONOHALO, MONOCARBOXYLIC SATURATED ALIPHATIC ACID CONTAINING UP TO ABOUT EIGHT CARBON ATOMS; (B) A A FUSIBLE PHENOL-ALDEHLYDE CONDENSATE; AND (C) AN ORGANIC POLYEPOXIDE CONTAINING AN AVERAGE OF MORE THAN ONE OXIRANE GROUP AND BEING FREE OF GROUPS REACTIVE WITH SAID AMIDE (A) AND SAID CONDENSATE (B) OTHER THAN HYDROXYL, CARBOXYL AND OXIRANE.
 6. THE COMPOSITION OF CLAIM 1 WHEREIN (C) IS A POLYFUNCTIONAL EXPOXIDIZED ESTER OF AN ETHYLENICALLY UNSATURATED NATURAL FATTY OIL ACID CONTAINING ABOUT 15-22 CARBON ATOMS, AND BEING FREE OF GROUPS REACTIVE WITH SAID ACID AMIDE (A) AND SAID CONDENSATE (B) OTHER THAN OXIRANE. 